Polymeric supported catalysts

ABSTRACT

This invention relates to a catalyst system comprising a substituted, bridged bisindenyl metallocene supported on a polymeric support wherein the metallocene is activated for polymerization by an ionizing reaction and stabilized in cationic form with a noncoordinating anion. A protonated ammonium salt of a noncoordinating amine is covalently bonded to the support. Propylene polymers produced by these supported catalyst systems have melting points and polymer microstructures similar to propylene polymers produced using analogous unsupported catalyst systems.

This application is a continuation-in-part of U.S. Ser. No. 09/092,752,filed Jun. 5, 1998, now U.S. Pat. No. 6,100,214, which application inturn claims priority of U.S. Ser. No. 60/048,965, filed Jun. 6, 1997 andU.S. Ser. No. 60/079,569, filed Mar. 27, 1998.

TECHNICAL FIELD

This invention relates to a catalyst system comprising a substituted,bridged indenyl metallocene supported on a polymeric support wherein themetallocene is activated for polymerization by an ionizing reaction andstabilized in cationic form with a noncoordinating anion. Propylenepolymers produced by these supported catalyst systems having meltingpoints and polymer microstructures similar to propylene polymersproduced using analogous unsupported catalyst systems.

BACKGROUND

The use of ionic catalysts for olefin polymerization whereorganometallic transition metal (i.e., metallocene) cations arestabilized in an active polymerization state by compatible,noncoordinating anions is a well-recognized field in the chemical arts.Typically such organometallic transition metal cations are the chemicalderivatives of organometallic transition metal compounds having bothancillary ligands which help stabilize the compound in an activeelectropositive state, and labile ligands at least one of which can beabstracted to render the compound cationic and at least one of which ofwhich is suitable for olefin insertion. Technology for supporting theseionic catalysts is also known.

U.S. Pat. No. 5,427,991 describes the chemical bonding ofnoncoordinating anionic activators to supports to prepare polyanionicactivators that, when used with the metallocene compounds, avoidproblems of catalyst desorption experienced when ionic catalystsphysically adsorbed on inert supports are utilized in solution or slurrypolymerization. The supports are derived from inert monomeric,oligomeric, polymeric or metal oxide support which have been modified toincorporate chemically bound, noncoordinating anions.

The preparation of polyanionic activators from hydrocarbyl compoundsentails a number of reactions. A typical reaction for a polymeric corecomponent begins with use of the lithiating agent n-BuLi, or optionallylithiating polymerizable monomers followed by polymerization of monomersinto a polymeric segment to produce a polymer or cross-linked polymerhaving pendant hydrocarbyl lithium groups. These are subsequentlytreated with the bulky Lewis acid trisperfluorophenylboron (B(pfp)₃) andsubjected to an ion exchange reaction with dimethylaniliniumhydrochloride ([DMAH]⁺[Cl]⁻) which results in a polymer surface havingcovalently linked activator groups of [DMAH]⁺[(pfp)₃BP]⁻, where P is thepolymeric core component.

Another method for attaching a noncoordinating anion activator to thesupport is described and detailed herein. An aminated polymer isprepared for example by treating a cross-linked polystyrene with adimethyl amine. The polymer bound amine is then quarternized by iontransfer from [PhNMe₂H][B(C₆F₅)₄]. The resulting support has covalentlylinked activator groups of [PNMe₂H][B(C₆F₅)₄] where P is again thepolymeric core component.

The functionalization of polymer resin beads for use with or preparationof heterogeneous catalytic species is also known. See, e.g., Fréchet, J.M. J., Farrall, M. J., “Functionalization of Crosslinked Polystyrene byChemical Modification”, Chemistry and Properties of CrosslinkedPolymers, 59-83 (Academic Press, 1977); and Sun, L., Shariati, A., Hsu,J. C. , Bacon, D. W., Studies in Surface Science and Catalysis 1995, 89,81, and U.S. Pat. No. 4,246,134 which describes polymeric carriers ofmacroporous copolymers of vinyl and divinyl monomers with specificsurface areas of 30 to 70 m²/g and the use of such for vinyl monomerpolymerization.

In gas phase and slurry polymerization, the use of supported orheterogeneous catalysts increases process efficiencies by assuring thatthe forming polymeric particles achieve a shape and density thatimproves reactor operability and ease of handling. However, substituted,bridged indenyl type metallocenes, supported on silica or polymersupports, have long been observed to produce polypropylenes with moreregio defects and subsequently shorter meso run lengths as determined by¹³C NMR compared to polymers produced by the respective unsupportedmetallocenes in solution. These defects result in a decrease in thepolymer melting point which is undesirable for many applications. Thisinvention provides a means for minimizing or even eliminating thedecreased stereospecificity normally observed when using thesemetallocenes in supported form. Consequently, the propylene polymers ofthis invention have fewer defects and higher melting points than thosepreviously obtainable in commercial processes. This achievementrepresents a significant advantage for polymer producers and theircustomers.

SUMMARY OF THE INVENTION

This invention relates generally to polymerization catalyst compositionscomprising the reaction product of a) a polymeric support functionalizedwith a protonated ammonium salt of a noncoordinating anion and b) one ormore substituted, bridged indenyl metallocene compounds.

DESCRIPTION OF THE INVENTION

As used herein the term “isotactic propylene polymer” means ahomopolymer, copolymer or terpolymer comprising at least 50% propyleneunits having at least 60% isotactic pentads according to analysis by ¹³CNMR.

As used herein the term “regio defect” means the insertion of themonomer unit in the opposite direction relative to the prevailinginsertion direction. With propylene as an example, with the methylenecarbon labeled as 1 and the ethylene carbon labeled as 2, themisinsertion would be that of a 2,1 insertion relative to the usual 1,2insertion.

As used herein the term “stereo defect” means the insertion of themonomer unit in the opposite chiral handedness as that of previouslyinserted units. Two monomer units inserted with the same handedness aresaid to be a meso diad. Whereas, two monomer units inserted in theopposite handedness are said to be a racemic diad. A succession of meodiads constitutes an isotactic sequence. A succession of racemic diadsconstitutes a syndiotactic sequence.

As used herein the term “mis-insertion” means insertions resulting ineither regio or stereo defects.

The invention olefin polymerization catalyst composition is the productof the reaction achieved by contacting a suitable functionalizationaromatic polymeric support according to formulas I or II with one ormore substituted, bridged indenyl metallocenes which are described inmore detail below. This product is as supported ionic catalystcomposition having a substituted, bridged indenyl cation and acomplementary noncoordinating anion, this composition being preferablyhomogeneously dispersed in the polymer support matrix. Additionally,without intending to being bound hereby, it is believed that thereexists a dative interaction between the transition metal cation and theamine functionality of the polymeric support matrix. The strength ofthis interaction should depend on the Lewis acidity of the transitionmetal cation and especially the Lewis basicity of the aminefunctionality. This interaction would act to reduce any tendency of theionic catalyst species to desorb from the polymer support matrix. Itwill be noted that extremely strong Lewis bases and/or Lewis bases withminimal steric bulk are known to strongly coordinate to the vacantcoordination site at the cationic metal center (e.g., pyridine). Ingeneral, this means that secondary amines are preferred over primaryamines.

The functionalized aromatic polymeric supports suitable for thisinvention comprise a protonated ammonium salt functionality covalentlybound to a polymeric support material which is preferably an aromaticpolymeric support material.

The nitrogen atom of the protonated ammonium salt functionality issubstituted with one to three groups at least one of which links theammonium functionality to the polymeric support as represented byformula I or II.

[Polymer-(R¹)—N(R²)(R³)H]⁺[NCA]  I

Polymer-B(pfp)₃ ⁻(R¹)(R²)(R³)NH⁺  II

where R¹ and where R¹ in formulas I or II can be hydrocarbyl orsubstituted hydrocarbyl, R² and R³ in formulas I or II may be the sameor different and are selected from the groups consisting of: hydrogen,hydrocarbyl, and a substituted hydrocarbyl. Preferably, R¹, R² and R³contain 1 to 30 carbon atoms, more preferably 1 to 20. As used herein,the term “substituted hydrocarbyl” means hydrocarbyl radical wherein oneor more of the hydrogen atoms of the hydrocarbyl radical R¹, R² and R³are replaced by a member of the groups selected from: halogens; asubstantially hydrocarbyl group containing from 1 to 3 heteroatomsselected from the group consisting of N, O, S, and P; a hydrocarbylsubstituted organometalloid; a halogen substituted organometalloid; andan organometalloid substituted with at least one substantiallyhydrocarbyl group containing from 1 to 3 heteroatoms selected from thegroup consisting of N, O, S, and P. NCA refers to a compatible“noncoordinating anion”.

The R¹, R² and R³ groups of the ammonium salts include those wherein twoor three R groups are joined to form an alicyclic or aromatic ringhaving a ring nitrogen atom. For example:

As used herein the term “noncoordinating anion” or “NCA” means an anionwhich, when associated with a transition metal cation, either does notcoordinate to the transition metal cation or which is only weaklycoordinated to said cation thereby remaining sufficiently labile to bedisplaced by a neutral Lewis base under polymerization conditions.“Compatible” noncoordinating anions are those which are not degraded toneutrality under polymerization conditions when the complexes betweenthem and the transition metal cationic catalyst compounds are formed.Further, the anion will not transfer an anionic substituent or fragmentto the cation so as to cause it to form a neutral four coordinates metalcompound and a neutral by-product from the anion under polymerizationconditions. As used herein, the term “transition metal cation” means thecation created when a ligand is abstracted from a transition metalcomplex.

Noncoordinating anions most useful in accordance with this invention arethose which compatible, stabilize transition metal cation in the senseof balancing its ionic charge, yet retain sufficient lability to permitdisplacement by an olefinically unsaturated monomer duringpolymerization. Additionally, the anions most useful in this inventionwill be of sufficient molecular size to partially inhibit, or help toprevent, neutralization of the transition metal cation by Lewis basesother than the polymerizable monomers that may be present in thepolymerization process. Suitable noncoordinating anions are describedin, for example, U.S. Pat. Nos. 5,198,401, 5,278,119, 5,407,884,5,599,761, (each fully incorporated herein by reference) preferably theywill be labile proton-containing, nitrogen-based salts described inthese documents.

Particularly preferred NCAs are those represented by the formula:

[BAr₁Ar₂X₃X₄]⁻

wherein:

B is boron in a valence state of 3;

Ar₁ and Ar₂ are the same or different substituted-aromatic hydrocarbonradicals which radical may be linked to each other through a stablebridging group;

and X₃ and X₄ are independently selected from the group consisting ofhydride radicals, halide radicals, hydrocarbyl radicals,substituted-hydrocarbyl radicals and organometalloid radicals.

Preferably, at least one of Ar₁ and Ar₂ are substituted with a fluororadical, more preferably perfluorophenyl radicals. Preferably, X₃ isalso a perfluorophenyl radical and X₄ is either a perfluorophenylradical or a straight or branched alkyl radical.

The polymeric support comprises polymeric compound which may be anyhydrocarbon based polymeric compound. Preferably the support is anaromatic hydrocarbon polymeric compound which has a surface area in therange of from about 1-400 m²/g, more preferably less than about 20 m²/gand most preferably 10 m²/g of less so as to avoid excessive monomeraccess to the active catalyst sites, which sites are essentiallyuniformly distributed throughout the mass of the support by virtue ofthe randomly incorporated functional groups on the polymeric chainsmaking up the support.

Porosity is measured as a single point nitrogen B.E.T. (Brunauer, S.,Ehmmet, P. H., Teller, E., JACS 1938, 60, 309) and can be exemplified bythe use of polystyrene based beads or gels. These beads or gels arelightly cross-linked and randomly functionalized with the ammonium saltcompounds. Thus the support should be insoluble under normalpolymerization operating conditions. Preferably the support is in theform of spheres of uniform dimension having a normal size range between100 and 400 US Mesh sizing (30 to 100 micrometers).

Suitable functionalized, aromatic polymeric supports can be obtainedcommercially, e.g., polystyrene beads or gels, or prepared syntheticallyin accordance with general knowledge in the art. The preferred supportof this invention are crosslinked polystyrene beads and gels produced byemulsion polymerization techniques. Examples of commercial products arethe Advanced Polymer Systems Microsponge® and the Johns-ManvilleChromosorb®. Functionalized hydrocarbon polymers such as but not limitedto halogenated or aminated polypropylene or polyethylene produced frommetal oxide supported or metal halide supported transition metalcatalysts are also possible supports.

Support synthesis generally consists of the copolymerization of vinylmonomers with comonomers having functionalization suitable fornucleophilic substitution by ammonium salts either by directcopolymerization or by copolymerization and subsequent chemical reactionthat places the appropriate functional groups according to Formulas I orII on the hydrocarbon polymeric chains making up the supports. Aspecific example is polystyrene-divinylbenzene copolymer gel or beads.The relative strength, i.e., resistance to fracture, is provided by thecontent of divinylbenzene (DVB) comonomer (weight %), commerciallyavailable products contain from 2 to 20 wt. % DVB. The higher ranges ofDVB, e.g., 10 to 20 wt. %, provide additional strength but the resultingadditional crosslinking may hinder kinetics by making the bead resistantto the shrinking and swelling necessary for normal polymerizationoperations. The effective porosity is adjustable by selection ofdivinylbenzene content. For example, DVB contents of 5 to 10 wt % canyield restricted polymerization kinetics suitable for high activitypolymerization catalysis, DVB contents of 1 to 5 wt. % can provide lessrestricted polymerization kinetics suitable for lower activitypolymerization catalysis. The term “high activity” relates to catalystsystems capable of activities greater than about 1×10⁷g-polymer/mol.-transition metal compound-atm-hr and “low activity” canbe understood as below about that amount.

Compound I can be prepared from the corresponding neutral amine definedin formula III:

Polymer-(R¹)(R²)(R³)N   III

(all of R¹, R² and R³ defined above) by either protonation by a molarexcess of an acid H⁺X⁻ followed by ion exchange with a salt of acompatible noncoordinating anion M′⁺NCA⁻. In the most general terms M′⁺can be any cationic species and X⁻ any anionic species. It will beobvious to one skilled in the art that H⁺X⁻ should be chosen so as tohave a lower pK_(a) value than the conjugate acid of II. AdditionallyM′⁺ and X⁻ should be chosen so that the byproduct of the ion exchangereaction, M′⁺X⁻, is either soluble in the reaction solvent chosen or acompatible wash solvent. Representative non-limiting examples ofsuitable X⁻ groups include halide, chlorate, perchlorate, triflate,perhaloborate, perhaloantimonate. Representative non-limiting examplesof suitable M′⁺ groups include alkali metal cations and ammoniumcations. Finally it should be noted that the protonation of amines toyield ammonium salts is a technique well known in the art, simplifyingthe selection of H⁺X⁻. Preferably the product of I can be prepared in asingle reaction by reacting the product of II with the ammonium salt ofa compatible noncoordinating anion, R⁴R⁵R⁶NH⁺NCA⁻. R⁴, R⁵, and R⁶ arechosen from the same group of radicals as R¹, R² and R³ above, with theadditional criterion that they should be chosen so as to yield anammonium salt with a lower pK_(a) value than that of the product of Iabove. Methods to calculate pK_(a) are well known in the art, andexperimentally measured pK_(a) are known for a variety of amines. Thisprovides knowledge of general guiding principles on the part of thoseskilled in the art (e.g., aryl substituents lower pK_(a) relative toalkyl substituents). See, for example, Perrin, D. D., Dempsey, S.,Serjeant, E. P., pK _(a) Predictions for Organic Acids and Bases(Chapman and Hall, London, 1981). Suitable solvents include aliphaticand aromatic hydrocarbons, ethers (including cyclic ethers) andhalocarbons (both aliphatic and aromatic hydrocarbons).

The compound of II can be prepared from the direct copolymerization ofthe functionalized monomer with the monomeric precursors of thepolymeric support. Specifically para-dimethylaminostyrene can beco-polymerized with styrene and divinylbenzene to yield the aminefunctionalized precursor of the invention catalyst. Preferably II can beprepared from a functionalized polymeric precursor III:

Polymer-Y   III

wherein Y is a functional group known to be readily convertible to theamine functionality R¹R²R³N— described above. Methods for converting awide variety of functional groups to the amine functionality are wellknown in the art, suitable functional groups include but are not limitedto: Alkanes, alkenes, alkyl halides, aryl halides, azides, nitrocompuonds, alcohols, aldehydes and ketones, nitriles, andorganometalloids (for a general discussion see T. C. Larock,“Comprehensive Organic Transformations: a guide to functional grouppreparations”, pgs. 385-438, (VCH publishers, 1989)).

Since there are many reactions of the types described above (synthesisof amines, protonation of amines, ion exchange) known in the art,reactions which proceed with high selectivity and with essentiallyquantitative yields, the polymeric supported activators can be readilyproduced in essentially pure form, i.e., as single molecular structureswithout any significant amount of reaction by-products. Infraredspectroscopy provides a useful analytical method for monitoring theextent of the reaction to optimize reaction conditions, further assuringa high purity product. Specifically, commercially availablechoromethylated polystyrene-co-divinylbenzene beads can be treated witha variety of dihydrocarbyl secondary amines to form weakly basic anionexchange resin, corresponding to precursor II, Reaction of thesematerials with dimethylanilinium tetrakis(perfluorophenyl) borate yieldsa compound of type I, the protonated ammonium salt functionalizedpolymeric support.

The reaction between the support and the metallocene should be conductedto facilitate permeation of the metallocene into the matrix of thepolymeric support. Preferably, therefore, supported activator particlesare treated with a solution of the metallocene. Suitable solvents forthe metallocene may be aliphatic or aromatic, depending upon theligation, the chemical composition of the support material, and thedegree of crosslinking of the support. Toluene and hexane are typical.It is particularly desirable to use a solvent to swell the support whenit has a surface area at or below about 50 m²/g. The reactiontemperature and pressure can vary so long as the reactants, solvents andthe carrier are neither degraded nor rendered unreactive. Ambientconditions are suitable. The resulting activation by protonation andstabilization with the noncoordinating anions is well known.

A mixture of two or more metallocenes may be used to tailor polymercomposition distribution. One solution containing all of themetallocenes should be made and all of the metallocenes should becompletely dissolved. Sequential additional of metallocenes orinsufficient dissolution of one or more of the metallocenes may resultin a inhomogeneous distribution of active centers within the catalystgranule.

The “substituted, bridged indenyl” are defined to mean metallocenes,i.e., transition metal compounds, which are consistent with the formula:

wherein M is a metal of Group 4, 5, or 6 of the Periodic Tablepreferably zirconium, hafnium and titanium, most preferably zirconium;

R¹ and R² are identical or different, preferably identical, and are oneof a hydrogen atom, a C₁-C₁₀ alkyl group, preferably a C₁-C₃ alkylgroup, a C₆-C₁₀ aryl group, preferably a C₆-C₈ aryl group, a C₆-C₁₀aryloxy group, preferably a C₆-C₈ aryloxy group, a C₂-C₁₀ group,preferably a C₂-C₄ alkenyl group, a C₇-C₁₀ arylalkyl group, preferably aC₇-C₁₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, preferably a C₇-C₁₂alkylaryl group, a C₈-C₄₀ arylalkenyl group, preferably a C₈-C₁₂arylalkenyl group.

R⁵ and R⁶ are identical or different, preferably identical, are one of ahalogen atom, preferably a fluorine, chlorine or bromine atom, a C₁-C₁₀alkyl group, preferably a C₁-C₄ alkyl group, which may be halogenated, aC₆-C₁₀ aryl group, which may be halogenated, preferably a C₆-C₈ arylgroup, a C₂-C₁₀ alkenyl group, preferably a C₂-C₄ alkenyl group, aC₇-C₄₀-arylalkyl group, preferably a C₇-C₁₀ arylalkyl group, a C₇-C₄₀alkylaryl group, preferably a C₇-C₁₂ alkylaryl group, a C₈-C₄₀arylalkenyl group, preferably a C₈-C₁₂ arylalkenyl group, a —NR₂ ¹⁵,—SR¹⁵, —OR¹⁵, —OSiR₃ ¹⁵ or —PR₂ ¹⁵ radical, wherein R¹⁵ is one of ahalogen atom, preferably a chlorine atom, a C₁-C₁₀ alkyl group,preferably a C₁-C₃ alkyl group, or a C₆-C₁₀ aryl group, preferably aC₆-C₉ aryl group;

—B(R¹¹)—; ⁻Al(R¹¹)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹¹)—, —CO—,—P(R¹¹)—, or —P(O)(R¹¹)—;

wherein:

R¹¹, R¹² and R¹³ are identical or different and are a hydrogen atom, ahalogen atom, a C₁-C₂₀ alkyl group, preferably a C₁-C₁₀ alkyl group, aC₁-C₂₀ fluoroalkyl group, preferably a C₁-C₂₀ fluoroalkyl group, aC₆-C₃₀ aryl group, preferably a C₆-C₂₀ aryl group, a C₆-C₃₀ fluoroarylgroup, preferably a C₆-C₂₀ fluoroalkyl group, a C₁-C₂₀ alkoxy group,preferably a C₁-C₁₀ alkoxy group, a C₂-C₂₀ alkenyl group, preferably aC₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, preferably a C₇-C₂₀arylalkyl group, a C₈-C₄₀ arylalkenyl group, preferably a C₈-C₂₂arylalkenyl group, a C₇-C₄₀ alkylaryl group, preferably a C₇-C₂₀alkylaryl group or R¹¹ and R¹², or R¹¹ and R¹³, together with the atomsbinding them, can form ring systems;

M² is silicon, germanium or tin, preferably silicon or germanium, mostpreferably silicon;

R⁸ and R⁹ are identical or different and have the meanings stated forR¹¹;

m and n are identical or different and are zero, 1 or 2, preferably zeroor 1, m plus n being zero, 1 or 2, preferably zero or 1; and

the radicals R³, R⁴, and R¹⁰ are identical or different and have themeanings stated for R¹¹, R¹² and R¹³. Two adjacent R¹⁰ radicals can bejoined together to form a ring system, preferably a ring systemcontaining from about 4-6 carbon atoms.

Alkyl refers to straight or branched chain substituents. Halogen(halogenated) refers to fluorine, chlorine, bromine or iodine atoms,preferably fluorine or chlorine.

Particularly preferred substituted, bridged indeny compounds of thestructures (A) and (B):

wherein:

M¹ is Zr or Hf, R¹ and R² are methyl or chlorine, and R⁵, R⁶R⁸, R⁹, R¹⁰,R¹¹ and R¹² have the above-mentioned meanings.

These chiral metallocenes may be used as a racemate for the preparationof highly isotactic polypropylene copolymers. It is also possible to usethe pure R or S form. An optically active polymer can be prepared withthese pure stereoisomeric forms. Preferably the meso form of themetallocene is removed to ensure the center (i.e., the metal atom)provides stereoregular polymerization. Separation of the stereoisomerscan be accomplished by known literature techniques. For special productsit is also possible to use rac/meso mixtures.

Illustrative but non-limiting examples of preferred substituted, bridgedindenyls include:

Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH₃)₂

Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zr(CH₃)₂;

Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zr(CH₃)₂;

Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zr(CH₃)₂;

Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,

1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,

1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2,4-dimethyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH₃)₂,

1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,

1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,

1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,

1,2-Ethandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,

Diphenylsilandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,

1,2-Butandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-ethyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH₃)₂,

Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl)Zr(CH₃)₂,

Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zr(CH₃)₂, and the like.

These and other preferred substituted, bridged indenyl compounds aredescribed in detail in U.S. Pat. Nos. 5,145,819; 5,243,001; 5,239,022;5,329,033; 5,296,434; 5,276,208; 5,672,668; 5,304,614 and 5,374,752; andEP 549 900 and 576 970 all of which are herein fully incorporated byreference.

Additionally, metallocenes such as those described in U.S. Pat. No.5,510,502, U.S. Pat. No. 4,931,417, U.S. Pat. No. 5,532,396, U.S. Pat.No. 5,543,373, WO 98/014585, EP611 773 and WO 98/22486 (each fullyincorporated herein by reference) are suitable for use in thisinvention.

Generally, the polymeric support should contains from about 0.01 to 0.7meq. substituted, bridged indenyl compound per gram polymer, morepreferably 0.01 to 0.3 meq. The polymeric supported cocatalyst activatorshould contain 0.01 to 0.9 meq. metal atom per gram of polymer,preferably from about 0.02 to about 0.3 meq. metal patom per gram ofpolymer.

When using the supported ionic catalysts of the invention, the totalcatalyst system can additionally comprise one or more scavengingcompounds. The term “scavenging compound” means those compoundseffective for removing impurities from the reaction environment.Impurities can be inadvertently introduced with any of thepolymerization reaction components, particularly with solvent, monomerand catalyst feed. Impurities can result in decreased, variable or evenelimination of catalytic activity. Typical impurities include water,oxygen, metal impurities, etc.

Typically the scavenging compound will be an organometallic compoundsuch as the Group 13 organometallic compounds of U.S. Pat. Nos.5,153,157, 5,241,025 and WO-A-93/14132, WO-A-94/07927, and that ofWO-A-95/07941. Exemplary compounds include triethyl aluminum, triethylborane, triisobutyl aluminum, methylalumoxane, isobutyl aluminoxane, andtri(n-octyl)aluminum. Those scavenging compounds having bulky or C₈-C₂₀liner hydrocarbyl substituents covalently bound to the metal ormetalloid center being preferred to minimize adverse interaction withthe active catalyst. The amount of scavenging agent to be used withsupported transition-metal cation-noncoordinating anion pairs isminimized during polymerization reactions to that amount effective toenhance activity.

The catalyst compositions of this invention may be used in a widevariety of polymerization processes to prepare a wide variety ofpolymers, but these catalyst compositions particularly suitable forpropylene polymerization. Any process may be used but propylenepolymerization are most commonly conducted using a slurry processes inwhich the polymerization medium can be either a liquid monomer, likepropylene, or a hydrocarbon solvent or diluent, propane, isobutane,hexane, heptane, cyclohexane, etc. or an aromatic diluent such astoluene. The polymerization temperatures may be those considered low,e.g., less than 50° C., preferably 0° C.-30° C., or may be in a higherrange, such as up to about 150° C., preferably from 50° C. up to about80° C., or at any ranges between the end points indicated. Pressures canvary from about 100 to about 700 psia (0.76-4.8 MPa. Additionaldescription is given in U.S. Pat. Nos. 5,274,056 and 4,182,810 and WO94/21962 which are fully incorporated by reference.

Propylene homopolymers may be formed with this system using conventionalbatch slurry techniques. The microstructure of the homopolymer willpreferably possess a meso run length as measured by 13C NMR 65% orgreater relative to that produced with the unsupported metallocenecatalyst. Copolymers with ethylene may be formed by introduction ofethylene to the propylene slurry or gas phase polymerization of gaseouspropylene and ethylene comonomers. Copolymers with ethylene preferablycontain 0 to 10 wt % comonomer. Stereoregular homopolymers andcopolymers of α-olefins may be formed with this system by introductionof the appropriate monomer or monomers to a slurry or bulk propyleneprocess.

EXAMPLES

Unfunctionalized polystyrene-co-divinylbenzene beads (1% DVB, 200-400mesh) were supplied by Biorad Laboratories (Hercules, Calif.) and washedcarefully prior to use. Chloromethylated beads were acquired from Biorad(4.0 meq Cl/g 200-400 mesh; and 1.35 meq Cl/g, 200-400 mesh) and AcrosOrganics (Pittsburg, Pa.) (0.4 meq Cl/g, 100-200 mesh) and either usedas received or subjected to a modification of the above washingprocedure in which the initial heated washing stages were replaced by ½h in aq. K₂CO₃ to avoid hydrolysis. CH₂Cl₂ was degassed by bubblingargon for ½ h prior to use. Other solvents and reagents were used asreceived. Low functionalization choromethylated beads (0.15 meq Cl/g)were prepared by the method of J. T. Sparrow, Tet. Lett., 1975, 53,4367. Slurry polymerizations were conducted in 1.25 L of bulk propylenewith triethylaluminum in a 2 L autoclave. Abbreviations in theseexamples include the following: THF (tetrahydrofuran), Ph (phenyl), Me(methyl), Bn (benzyl).

Differential scanning calorimetry (DSC) data was collected using aPerkin Elmer DSC-7. Approximately 6.0 mg of polypropylene granules wasmassed into a sample pan and the following thermal program was used. Thepolymer was annealed for 5 minutes at 200° C. It was subsequently cooledto 25° C. at a rate of 10° C./min. The temperature was held for 5minutes at 25° C. The sample was then heated to 200° C. at a rate of 10°C./min. The peak melting temperature was recorded.

¹³C NMR data was obtained at 100 MHz at 125° C. on a Varian VXR 400 NMRspectrometer. A 90° C. pulse, an acquisition time of 3.0 seconds, and apulse delay of 20 seconds was employed. The spectra were broad banddecoupled and were acquired without gated decoupling. Similar relaxationtimes and nuclear Overhauser effects are expected for the methylresonances of polypropylenes, which were the only homopolymer resonancesused for quantitative purposes. A typical number of transients collectedwas 2500. The sample was dissolved in tetrachlorethane-d2 at aconcentration of 15% by weight. All spectral frequencies were recordedwith respect to an internal tetramethylsilane standard. In the case ofthe polypropylene homopolymer, the methyl resonances were recorded withrespect to 21.81 ppm for mmmm, which is close to the reported literaturevalue of 21.855 ppm for an internal tetramethylsilane standard. Thepentad assignments used are well established.

[PS—CH₂N(CH₃)₂H]⁺[B(C₆F₅)₄]⁻

Chloromethylated polystyrene-co-divinylbenzene beads with loadings of0.14-4.0 Cl/g were swollen in a solution of dimethylamine in THF (2M,Aldrich), and stirred for two days at room temperature. They were thenrinsed with THF, THF/water 2:1, THF/water 1:2, water (twice), THF/water1:2, THF/water 2:1, THF (twice) and dried under vacuum at 60° C.overnight. The aminated beads were treated with a 0.07 M solution of[PhNMe₂H][B(C₆F₅)₄] in CH₂Cl₂ (1.5 equivalents) for 1.5 hr, and thenfiltered and rinsed with CH₂Cl₂ (4 times) to yield beads with boronloadings of 0.15-1.1 meq. boron/g. Boron loadings were evacuatedgravimetrically and by an IR assay. These beads were then treated with avariety of Group 4 metallocenes to generate the active catalytic speciesat loadings of 0.14-0.7 meq. catalyst/gram of beads. The metalloceneloadings were approximated on the basis of quantitative reaction ofmetallocene with borated bead. Borated beads were typically treated with3 equivalents of metallocene compound.

[PS—CH₂NPh(CH₃)H]⁺[B(C₆F₅)₄]⁻

Chloromethylated polystyrene-co-divinylbenzene beads with loadings of0.4-4.0 meq. Cl/g were swollen in neat N-methylaniline and stirred fortwo days at room temperature. They were then rinsed with THF, THF/water2:1, THF/water 1:2, water (twice), THF/water 1:2, THF/water 2:1, THF(twice) and dried under vacuum at 60° C. overnight. The aminated beadswere treated with a 0.07 M solution of [Ph₂NH₂][B(C₆F₅)₄] in CH₂Cl₂ (1.5equivalents) for 1.5 h, and then filtered and rinsed with CH₂Cl₂ (4times) to yield beads with boron loadings of 0.36-0.87 meq. boron/g.Boron loadings were evaluated gravimetrically after careful drying.

Example 1—Catalyst A Preparation

In an inert atmosphere glove box, 1.0 gram of the protonated ammoniumsalt activator [PS—CH₂N(CH₃)₂H]⁺[B(C₆F₅)₄]⁻ with 0.67 mmol availablefunctional group per gram of beads (i.e., 0.67 meq) prepared asdiscussed above was slurred in 20 mL of dry, oxygen free toluene at 25°C. under nitrogen in a 100 mL round bottom flask while stirring with amagnetic stirrer, followed by the addition of 0.076 g of dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl in small portions. Thereaction was stirred for 1 hour. 30 ml of pentane was added and themixture was stirred for several minutes. The solvent was decanted and 40ml of fresh pentane was added. After several minutes of stirring, thesolvent was decanted. The solid was vacuum dried overnight yielding0.802 g of finished catalyst. Final catalyst loading was calculated tobe 0.13 mmol of transition metal per gram of finished catalyst.

Example 2—Catalyst B Preparation

Catalyst B was prepared in analogous manner to Catalyst A, but 0.871grams of protonated ammonium salt activator [PS—CH₂N(CH₃)₂H⁺[B(C₆F₅)₄]⁻with 0.67 mmol available functional group per gram of beads (i.e., 0.67meq) was reacted with 0.076 g of dimethylsilylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium dimethyl yielding 0.706 gof finished catalyst (some material loss due to transfer), with acalculated loading of 0.13 mmol of transition metal per gram of finishedcatalyst.

Comparative Example 3—Catalyst C Preparation

In a nitrogen purged glove box, 0.18 gDimethylsilylbis(2-methyl-4-phenyl indenyl)zirconium was placed in a 100ml beaker with a mini stir bar. 9.3 g of a 30 % wt % solution ofmethylaluminoxane was added to the beaker. The mixture was stirred forone hour producing a red solution. The solution was added slowly to 10.0g of Davison 952 silica (calcined at 600° C.) with mechanical mixing.After the addition was complete the solid was vacuum dried. Yield: 12.47g. Final catalyst loading was calculated to be 0.022 mmol of transitionmetal per gram of finished catalyst.

Comparative Example 4—Catalyst D Preparation

In a nitrogen purged glove box, 180.5 g of Davison 952 silica (calcinedat 600° C.) was massed and placed in a 4 L 3 neck flask equipped with anoverhead stirrer. 1.5 L of dry toluene was added and the mixture wasslurried. 13.0 ml of N,N-diethyl aniline was added to the mixture. After5 minutes of stirring, 39.5 g of tris(pentafluorophenyl)boron was added.The mixture was stirred for one hour. 17.5 g ofDimethylsilylbis(2-methyl-4-phenyl indenyl)zirconium was added to themixture and it was stirred for 2 hours. After this time the stirring wasstopped and the solvent was decanted. The solid was vacuum dried. Yield:210 g. Final catalyst loading was found to be 0.127 mmol of transitionmetal per gram of finished catalyst.

Comparative Example 5—Catalyst E Preparation

In a nitrogen purged glove box, 1.97 g of Davison 952 silica (calcinedat 600° C.) was massed and placed in a 50 ml round bottom flaskcontaining a stir bar. 20 ml of toluene was added and the silica wasslurried. 0.14 ml of N,N-diethyl aniline was added to the mixture. After5 minutes of stirring, 0.429 g of tris(pentafluorophenyl)boron wasadded. The mixture was stirred for 1 hour. 0.15 g ofDimethylsilylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium dimethyl wasadded and the mixture was stirred for two hours. After this time, thesolvent was removed invacuo. Yield: 2.55 g. Final catalyst loading wasfound to be 0.078 mmol of transition metal per gram of finishedcatalyst.

Polymerization Example 1

A 2 L autoclave reactor was heat dried under nitrogen flow for 45minutes. 0.4 ml of a 1M solution of triethylaluminum solution in hexanewas introduced as a scavenger. 36 mmol of H₂ was added followed by 1050ml of propylene. The reactor temperature was raised to 70° C. 0.0413 gof catalyst A was flushed into the reactor with 200 ml of propylene. Thepolymerization mixture was stirred for 1 hour at 500 ppm. Thepolymerization was stopped by cooling the reactor and venting thepropylene. Yield: 242 g. Catalyst Efficiency: 5860 g PP/g catalyst, MeltFlow Rate: 23 dg/min. Tm: 155.1° C., MWD 3.87.

Polymerization Example 2

The reactor was prepared as in Example 1 except 0.6 ml of a 1M solutionof triethylaluminum solution and 25 mmol of H₂ were used. 0.041 g ofCatalyst B was flushed into the reactor with propylene to initiate thepolymerization. The polymerization mixture was stirred for 1 hour.Yield: 329 g, Catalyst Efficiency: 8020 g PP/g Catalyst, Melt Flow Rate:4.8 dg/min, Tm: 156.4° C., MWD 3.34.

Comparative Polymerization Example 3

The reactor was prepared as in Example 1 except 0.25 ml of a 1M solutionof triethylaluminum solution and 25 mmol of H₂ were used. 0.101 g ofCatalyst C was flushed into the reactor with propylene to initiate thepolymerization. The polymerization mixture was stirred for 1 hour.Yield: 272 g, Catalyst Efficiency: 2690 g PP/g Catalyst, Melt Flow Rate:1.6 dg/min, Tm: 152.8° C., MWD 4.27.

Comparative Polymerization Example 4

The reactor was prepared as in Example 1 except 0.25 ml of a 1M solutionof triethylaluminum solution and 25 mmol of H₂ were used. 0.037 g ofCatalyst D was flushed into the reactor with propylene to initiate thepolymerization. The polymerization mixture was stirred for 1 hour.Yield: 265 g, Catalyst Efficiency: 7160 g PP/g Catalyst, Melt Flow Rate:0.44 dg/min, Tm: 152.2° C., MWD 2.44.

Comparative Polymerization Example 5

The reactor was prepared as in example 1 except 0.25 ml of a 1M solutionof triethylaluminum solution and 25 mmol of H₂ were used. 0.041 g ofCatalyst E was flushed into the reactor with propylene to initiate thepolymerization. The polymerization mixture was stirred for 1 hour.Yield: 289 g, Catalyst Efficiency: 7050 g PP/g Catalyst, Melt Flow Rate:3.5 dg/min, Tm: 152.2° C., MWD 6.90.

Comparative Polymerization Example 6

The reactor was prepared as in Example 1 except 500 ml of dry hexane wasadded as a solvent. 0.25 ml of a 1M solution of triethylaluminumsolution, 149 mmol of H₂ and 500 ml of propylene were subsequentlyadded. The reactor temperature was increased to 70° C. 0.023 g ofDimethylsilylbis(2-methyl-4-phenyl indenyl)zirconium and 0.033 g ofN,N-dimethyl anilinium tetrakis(pentafluoro)borate were dissolved in 20ml of toluene. 2 ml of this solution was flushed into the reactor with250 ml of propylene. The polymerization mixture was stirred for 15minutes. The reaction was stopped by cooling the reactor and venting thepropylene. The hexane solvent was evaporated and the polymer was dryed.Yield: 17.0 g, Catalyst Efficiency: 4.3×10⁶ g PP/mmol Zr, Tm: 155, Mwe:37000, MWD: 1.74.

Polymerization Example 7

The reactor was prepared as in Example 1 except 0.4 ml of a 1M solutionof triethylaluminum solution and 25 mmol of H₂ were used. 0.041 g ofcatalyst A was flushed into the reactor with propylene to initiate thepolymerization. The polymerization mixture was stirred for 15 minutes.Yield: 28.8 g, Catalyst Efficiency: 699 gPP/g catalyst, Tm 155.6, Mw86000, MWD: 3.88.

Comparative Polymerization Example 8

The reactor was prepared as in Example 1 except 0.4 ml of a 1M solutionof triethylaluminum solution and 55 mmol of H₂ were used. 0.102 g ofCatalyst C was flushed into the reactor with propylene to initiate thepolymerization. The polymerization mixture was stirred for 1 hour.Yield: 230 g, Catalyst Efficiency: 2300 gPP/g catalyst, Tm 151.1, Mw189000, MWD: 7.08.

Comparative Polymerization Example 9

Catalyst D was fed into the continuous pilot reactor at 70° C. with ahydrogen setpoint of 5000 mppm. Catalyst Efficiency: 8600 gPP/gcat·hr.,Tm 152.3, MWD: 2.70. Molecular weight was 105,000.

TABLE 1 70° C. Propylene Polymerization Results Hydrogen EfficiencyPoly. No. Support Metallocene Activator (mmol) (gPP/gCat) Tm (° C.) MwMWD 1 Polystyrene 2-methyl- Bound 25 5900 155.1  46 K 3.8 4-phenyl²anilinium 2 Polystyrene 2-methyl bound 25 8000 156.97 NA NA 4-nephthyl³anilinium 3 (comp.) Silica 2-methyl MAO 25 2700 152.8 320 K 4.274-phenyl Cl₂ ⁴ 4 (comp.) Silica 2-methyl Bound 25 7100 152.2 460 K 2.444-phenyl anilinium 5 (comp.) Silica 2-methyl bound 25 7100 152.2 298 K6.90 4-naphtyyl anilinium 6 (comp.) None 2-methyl DMAH⁵ 149  4.3 × 10¹155  37 K 1.74 4-naphthyl 7 Polystyrene 2-methyl bound 25  699 155.6  86K 3.88 4-phenyl anilinium 8 (comp.) Silica 2-methyl MAO 55 2300 151.1189 K 7.08 4-phenyl Cl₂ 9 (comp.) Silica 2-methyl bound 5000  8600 152.3105 K 2.70 4-phenyl anilinium (mppm) ¹gPP/mmol Zr ²dimethylsilylbis(2methyl-4-phenylindenyl)zirconium dimethyl ³dimethylsilylbis(2methyl-4-naphthylindenyl)zirconium dimethyl ⁴dimethylsilylbis(2methyl-4-phenylindenyl)zirconium dichloride ⁵N,N-dimethyl aniliniumtetrakis(perfluorophenyl)boron

TABLE 2 Amount of Defects from ¹³C NMR Poly- Stereo Regio Meso meriza-Metal- Defects/ defects/ Run tion Support locene Activator 10K 10KLength 6 none 2-methyl DMAH 34.4 20.8 181 4-phenyl 7 poly- 2-methylbound 27.3 45.4 137.6 styrene 4-phenyl anilinium 8 silica 2-methyl MAO19.9 80.0 100 4-phenyl 9 silica 2-methyl bound 19.2 75.4 106 4-phenylanilinium

While the present invention has been described and illustrated byreference to particular embodiments, it will be appreciated by those ofordinary skill in the art that the invention leads itself to manydifferent variations not illustrated herein. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

What is claimed is:
 1. An catalyst composition comprising the reactionproduct of a) a polymeric support functionalized with a covalentlybonded protonated ammonium salt of a noncoordinating anion and b) one ormore bridged, substituted indenyl metallocene compounds.
 2. The catalystcomposition of claim 1 wherein the support is an aromatic polymericsupport.
 3. The catalyst composition of claim 1 wherein the support ispolystyrene.
 4. The catalyst composition of claim 1 wherein themetallocene is represented by the formula:

wherein M is a metal of Group 4, 5, or 6 of the Periodic Table; R¹ andR² are identical or different, preferably identical, and are one of ahydrogen atom, a C₁-C₁₀ alkyl group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ arylalkyl group, aC₇-C₄₀ alkylaryl group, or a C₈-C₄₀ arylalkenyl group; R⁵ and R⁶ areidentical or different, and are one of a halogen atom, a C₁-C₁₀ alkylgroup which may be halogenated, a C₆-C₁₀ aryl group which may behalogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR₂ ¹⁵, —SR¹⁵, —OR¹⁵,—OSiR₃ ¹⁵ or —PR₂ ¹⁵ radical, wherein R¹⁵ is one of a halogen atom, aC₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;

—B(R¹¹)—; ⁻Al(R¹¹)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹¹)—, —CO—,—P(R¹¹)—, or —P(O)(R¹¹)—; wherein: R¹¹, R¹² and R¹³ are identical ordifferent and are a hydrogen atom, a halogen atom, a C₁-C₂₀ alkyl group,a C₁-C₂₀ fluoroalkyl group, a C₆-C₃₀ aryl group, a C₆-C₂₀ fluoroalkylgroup, a C₁-C₂₀ alkoxy group, a C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkylgroup, a C₈-C₄₀ arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹¹ andR¹², or R¹¹ and R¹³, together with the atoms binding them, form one ormore ring systems; M² is silicon, germanium or tin; R⁸ and R⁹ areidentical or different and have the meanings stated for R¹¹; m and n areidentical or different and are zero, 1 or 2, m plus n being zero, 1 or2; and the radicals R³, R⁴, and R¹⁰ are identical or different and havethe meanings stated for R¹¹, R¹² and R¹³ or two adjacent R¹⁰ radicalsare joined together to form a ring system.
 5. The catalyst compositionof claim 1 wherein the metallocene is selected from the group consistingof: Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH₃)₂Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zr(CH₃)₂;Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zr(CH₃)₂;Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zr(CH₃)₂;Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2,4-dimethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,Diphenylsilandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,1,2-Butandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-ethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl)Zr(CH₃)₂, andDimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zr(CH₃)₂.
 6. Compositionsystem of claim 1 wherein the polymeric support is functionalized withan ammonium salt of a noncoordinating anion represented by the formula:[Polymer-(R¹)—N(R²)(R³)H]⁺[NCA] wherein R¹ and where R¹ in formulas I orII is hydrocarbyl or substituted hydrocarbyl, R² and R³ are the same ordifferent and are selected from the group consisting of: hydrogen,hydrocarbyl, and a substituted hydrocarbyl; and wherein NCA isrepresented by the formula: [BAr₁Ar₂X₃X₄]⁻ wherein: B is boron in avalence state of 3; Ar₁ and Ar₂ are the same of differentsubstituted-aromatic hydrocarbon radicals which, radicals may be linkedto each other through a stable bridging group; and X₃ and X₄ areindependently selected from the group consisting of hydride radicals,halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicalsand organometalloid radicals.
 7. The catalyst system of claim 1 whereinthe support is functionalized with a ammonium salt of a noncoordinatinganion selected from the group consisting of tetrakis perfluorophenylborate, tetrakis(3,5-di(tri-fluoromethyl)phenyl borate andtetrakis(di-t-butylmethylsilyl)perfluorophenyl borate.
 8. A catalystcomposition comprising the reaction product of a) an aromatic polymericsupport functionalized with a covalently bonded protonated ammonium saltof a noncoordinating anion selected from the group consisting oftetrakis perfluorophenyl borate, tetrakis(3,5-di(tri-fluoromethyl)phenylborate and tetrakis(di-t-butylmethylsilyl)perfluorophenyl borate and b)one or more metallocenes selected from the group consisting of:Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH₃)₂Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zr(CH₃)₂;Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zr(CH₃)₂;Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zr(CH₃)₂;Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2,4-dimethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,1,2-Ethandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,Diphenylsilandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,1,2-Butandiylbis(2-methyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-ethyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH₃)₂,Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH₃)₂,Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl)Zr(CH₃)₂, andDimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zr(CH₃)₂.
 9. A method forpolymerizing olefins comprising contacting one or more monomers undersuitable polymerization conditions in the presence of the catalystcompositions of claims 1 through 8.